Detergent composition



March 25, 1952 J. E. HANSON 2,590,613

, DETERGENT COMPOSITION Filed May 24, 1948 2 SHEETS-SHEET 1 DETERGENCY VS. CARBOXYL CONTENT OF ADDITIVE O Y z 120 I I Z C 115 n: LL] E no DATA= TAB E 111 O CO CENTRATION O.iZ/o(97/o- $U|..FONATE"SULFATE+3% ODlUM SALT OF CIILLURONIC ACID TEMPERATURE: 140 F 05 WQTER HARDNESSI 300pp M O 5 1O 15 2O 25 CARBOXYL CONTENT I FIG. 1

INVENTOR John 5. Hanson ATTORNE S March 25, 1952 J. E. HANSON DETERGENT COMPOSITION Filed May 24, 1948 2 SHEETS-SHEET 2 ON DETERGENCY 65 I DETERGENT A (.2%CONCENTR ATION) 2 6O LU m 55 DATA= T BLE II, TEMPERATURE! [40F 8 Vl/ATER HARDNESSE30OP|JM N 50 TA/DETERGENT B .2% CONCENTRATION 4o o 2 4 A s 8 IO l2 WEIGHT OF ADDITIVE CARBOXYL. CONTENT H.5-l8.5

- BY WT.

FIG. 2

INVENTOR John E. Harmon A r romwsrs Patented Mar. 25, 1952 DETERGENT COMPOSITION John E. Hanson, Richmond, Calif., assignor to California. Research Corporation, San Francisco, Califl, a corporation of Delaware Application May 24, 1948, Serial No. 28,853

Claims. (Cl. 252-461) The invention relates to improved detergent compositions comprising a water-soluble salt of celluronic acid and a surface-active organic detergent compatible therewith. More particularly, the invention involves improvement of noncationic, i. e., of anionic and non-ionic surfaceactive organic detergents, by incorporation of minor amounts of a water-soluble celluronic acid salt illustrated by salts of monovalent and bivalent cations. A presently preferred embodiment of the invention involves alkaryl sulfonatetype detergent compositions containing said salts.

This application is a continuation-in-part of my application, Serial No. 764,399, filed July 2 1947.

The term celluronic aci as used in this specification designates the product of selective or controlled oxidation wherein substantially only the primary hydroxyl group of anhydroglucose units in the cellulose molecule has undergone oxidation and this oxidation is carried to formation of a carboxyl group, as will be explained in great-- er detail hereinafter.

The term water-soluble salts of celluronic acids as used herein designates not only those salts which may form true Water solutions in the concentrations used in washing operations but also embraces salts which form stable aqueous dispersions which may not be true solutions as indicated by a cloudy appearance of the solution. Magnesium celluronate is an example of a water-soluble salt which forms cloudy solutions embraced by this invention.

According to the present invention, a remarkable and unexpected improvement of detergent properties is secured by intimately incorporating, as by dispersing or dissolving, a water-soluble salt of celluronic acid in a composition containing a. non-cationic surface-active organic detergent such as soap or a synthetic detergent of the anionic or non-ionic type. It has been found that a much greater degree of soil removal is secured in various washing operations because of the presence of such water-soluble celluronic acid salt additive in the detergent composition than is otherwise obtainable in the absence of such additive. A remarkable feature of the detergent compositions improved in accordance with the present invention is the small amount of the celluronic acid salt required to effect a significant improvement of detergency.

The aforementioned salts of celluronic acids responsible for the new and significant improvement of detergency are water-soluble salts prepared by the reaction of an aqueous solution or dispersion of a base, e. g., sodium hydroxide, magnesium hydroxide, organic amines such as pyridine, alkylamines and alkenylamines, ammonia, and quaternary ammonium hydroxides, upon celluronic acidthis particular derivative of cellulose being obtainable by the oxidation of cellulose fibers with nitrogen dioxide (NO2--N2O4) gases. The oxidized celluloses obtained in this oxida tion are known under the name of celluronic acids and, in contradistinction to other types of oxidized celluloses, are the products of a selective and controlled oxidation of cellulose. Through the application of particular oxidation techniques, as disclosed, for instance, in U. S. Patent No. 2,232,990 to Yackel et al., only the primary hydroxyl in each anhydrogl-ucose unit of the cellulose molecule is converted to a carboxyl group in the oxidation with NO2N2O4 gases, and the secondary hydroxyls remain particularly unaffected. Thus, cellulose is a long chain molecule containing a series of anhydroglucose rings illustrated by the following structural formula:

n dmon 11 (IJHQOH In celluronic acid at least a portion of the primary alcohol groups in the cellulose molecule is oxidized to a carboxyl group as illustrated in H OHH the following formula:

on H 011 H H +-'i\ H 0.44 t m /H t O cellulose by chain rupture is not precluded since the long-chain celluronic acid structure is retained in these derivatives.

For the purposes of this invention it is important, however, that the celluronic acid structure be retained by restricting the attack of the oxidant, i. e., of NO2N2O4, to the specific primary hydroxyl group in the celulose molecule. Degradation of the molecular chain by oxidation should be avoided to secure chemical homogeneity of the reaction product. Furthermore, by preventing the occurrence of a topochemically variable reaction, physical homogeneity of the product is obtained.

The selectivity of the NO2N2O4 oxidant for the primary hydroxyl of the anhydroglucose unit of cellulose permits of producing distinct and reproducible species of oxidized cellulose-- the celluronic acids. Depending on the extent of oxidation, the resulting celluronic acids represent (1) polymers of anhydroglucuronic acid units in the case where the selective oxidation of the primary hydroxyl group is substantially complete, or (2) copolymers of anhydroglucose and anhydroglucuronic acid units, in the case where only a part of anhydroglucose units have been selectively oxidized by NO2--N2O4 gases.

The completely oxidized celluronic acid has a theoretical carboxyl content of about 25.57% by weight based on the acid, while the celluronic acid with a carboxy content of about 13.3% is a polymer of equimolar amounts of anhydroglucose and anhydroglucuronic acid units. In general, all celluronic acids ar characterized by a high aifinity for dyes and readily absorb, e. g.,

methylene blue and rosaniline acetate.

Those celluronic acids which have a carboxyl content of more than about 11.5% by weight, though not directly soluble in water, form water-soluble salts with monovalent and bivalent cations. On the other hand, when the carboxyl content of celluronic acids is more than about 7% but less than about 11.5% by weight, they are either insoluble or partly insoluble in dilute (1-2%) alkalies.

Now it has been discovered that the aforementioned celluronic acids, when converted to water-soluble salts, by party or completely dissolving in dilute alkalies, or other monovalent or bivalent bases, e. g., in aqueous pyridine, or in an aqueous dispersion of magnesium hydroxide, form salts which bring about an unexpected improvement in detergency when added in small amounts to detergent mixtures. This improvement is remarkable, for these salts alone possess substantially no detergent effect when dissolved in water, notwithstanding the amounts used. While the addition of these salts or" celluronic acids to detergent compositions, for instance, to the alkaryl sulfonate mixtures, in amounts from about 0.5% by weight upwards, based on the total dry ingredients in the detergent mixture, results in an improvement of d..- tergency, it has been found that maximum effects are secured in such detergents with amounts of about 3% and usually not greater than about 5% by weight.

At this point it may be noted that the fore going proportions are based on total dry ingredients in the detergent composition. Alkaryl sulfonate detergents as well as other synthetic detergents and soap contain substantial proportions of builders. The proportions of these builders may vary widelyand, in the case of alkaryl sulfonates and other synthetic detergents, may comprise as much as 80% of the detergent composition. More conventional proportions are from about 60% to about of builder with from about 30% to about 40% of surface-active organic detergent. The foregoing proportions of water-soluble celluronic acid salts may be defined more directly by reference to the surface-active organic detergent component rather than the entire dry composition. Thus, 0.5% by weight on total dry ingredients corresponds to about 11.5% by weight based on the surface-active organic detergent. Likewise, the 3% by weight proportion may be expressed as an upper limit of from about 6% to about 9% based on the surfave-active detergent component. Again, 5% corresponds to from about 10% to about 15% by weight of the surface-active organic detergent above illustrated (alkaryl sulfonate type).

An additional unexpected discovery with respect to the water-soluble salts of celluronic acids is the fact that a remarkable improvement in detergency is secured by the use of salts with the carboxyl content in the operative range of from about 7% to about 20% by weight, and particularly in the critical range of from about 11.5% to about 18.5% by weight, that is, in the very range where celluronic acids become readily soluble in a 1% caustic solution.

It was indicated hereinabove that salts of celluronic acids may be prepared by reacting thereon with an aqueous solution of a base, e. g., dilute solution of sodium or potassium hydroxide, an aqueous dispersion of magnesium hydroxide, a solution of an amine, and the like. They may be also prepared by reacting celluronic acids with an aqueous solution of a salt of a weak acid such as sodium carbonate or acetate.

To prepare a detergent composition improved in accordance with the present invention, the salt of celluronic acid in an amount of at least 0.5%, and preferably 3%, and usually not greater than about 5%, by weight of the total dry ingredients in the detergent mixture, is intimately dispersed in the detergent mixture supplied in a suitable form, e. g., as a slurry or a solution. Water is added, if necessary, to obtain the desired concentration of the mixture, and the resulting composition dried, e. g., by drum-drying, and recovered as a product having dispersed therein the required amount of the celluronic acid salt additive.

The term dispersed as used hereinabove with respect to the mixture of water-soluble celluronic acid salts in the detergent, means intimately distributed as in the form resulting from colloidal dispersions, solutions, or emulsions within the detergent mixture. The dried particles, even though relatively small, are substanstantially uniform from particle to particle in detergent and celluronic acid content. This has the advantage that uniformity of composition is maintained during shipping and handling, and the problem of separation of celluronic acid salt particles from detergent particles by gravitation or classification, according to particle size, is substantially precluded. This characteristic is important both in finished detergents and in concentrates of water-soluble salts of celluronic acid hereinabove described.

The remarkable improvement in detergency brought about by dispersing a small amount of a water-soluble celluronic salt in a detergent composition is shown by the experimental data in Table I. The tests represented by these data and those of the subsequent tables, unless otherwise 'onic acid salt additive.

bonate) specified, are launderometer tests of soil removal from hard twisted cotton, the soil uniformly applied to the sample swatches of cotton being of an oily type (a paste of oil, tallow and carbon black). These tests are effected under conditions generally applied in common laundering procof the actual practice. Ihetemperature of the tests is about 140 F., though higher or lower temperatures do not affect the action of the cellur- The hardness of water in all tests, unless otherwise specified, is the average hardness of water throughout the United 'States (300 parts per million:200 parts of calcium carbonate 100 parts ofv magnesium car- In most tests, unless otherwise stated, 0.2% concentration of detergent mixture in water is used. 1

The several detergent compositions, which are used to compare the effect of an addition of the 'celluronic acid salt thereto with the detergency effects displayed without such an addition, in-

clude: a well-known anionic detergent composition comprising the salt of a half-ester of an alkenyl dicarboxylic acid designated as detergent X, an anionic mixture comprising sodium alkyl benzene sulfonate with 12 to 15 carbon atoms in the alkyl chain and produced by alkylating benzene with polypropene and designated as detergent A, a non-ionic alkyl phenol polyglycol ether composition designated as detergent Y, and an anionic sulfate of a fatty acid 'monoglyceride designated as detergent Z. Sodium salt of celluronic acid with a carboxyl content of 11.5% to 18.5% in an amount of by weight of the total dry ingredients of the detergent mixture is used.

The following procedure is followed in the launderometer tests of TableI and subsequent tables of this case, unless otherwise indicated. The uniformly soiled swatches of cotton are subjected in each instance to a series of 4 consecutive washings of 20 minutes duration, and the degree of whiteness obtained is measured in a photoelectric apparatus free of human equation. The detergency ratings in Table I are computed with reference to an arbitrarily chosen standard, namely, detergency (whiteness level) obtained with a 0.4% concentration of well-known soap D (fatty acid soap) in hard water (300 parts per million), taken to be equal 100 and designated as Soap Index.

Table I Soap index Alkaryl sulfonate (detergent A) 53 Alkaryl sulfonate (detergent A) +5% -additlve- 90 Alkenyl dicarboxylic acid (detergent X) :2: (59 Alkenyl dicarboxylic acid (detergent X) +5% additive 78 Non-ionic alkyl phenol polyglycol ether (detergent Y) 76 Non-ionic alkyl phenol polyglycol ether (deter gent Y) +5% additive 115 Anionic glyceryl sulfate (detergent Z) 72 by a hydrophilic group. In anionic detergents,

the hydrophilic group is an acid or acid-forming radical attached to the hydrophobic group and usually utilized in the form of a salt. Exemplary hydrophilic radicals are: COOM, SO3M, SO4M, and the like, where M is a water-soluble salt-forming group. Such detergents are termed anionic since it is the anionic portion of the molecule which is the primary surface-active and detergency component. Non-ionic detergents, as the term indicates, are characterized by a surfaceactive component which does not ionize. Nevertheless, the non-ionic detergents contain a hydrophobic group and a hydrophilic group to impart the requisite solubility and detergency activity. A common non-ionic hydrophobic group are the polyalkylene oxides such as the polyethylene oxide radicals:

where n is 3 to about 13 and R is a hydrophobic radical usually of hydrocarbon structure and containing, for example, from about 10 to about 20 carbon atoms. Accordingly, the following examples are to be taken merely as illustrative of the foregoing known types of detergents in which water-soluble salts of a celluronic acid may be incorporated in accordance with this invention.

Another series of tests is carried out under similar conditions as for tests in Table I, but using a 0.2% concentration of detergent in soft water (50 parts per million of hardness, of which is CaCOz and /3 is MgCOa). In this series, several other detergents are used, namely, a wellknown alkyl sulfate detergent designated as detergent B; a widely used type of soap D (fatty acid soap) mentioned hereinbefore; another alkyl benzene sulfonate detergent of commerce designated as detergent C; and an alkyl sulfonate composition designated as detergent E The results of these tests are given in Table II and point to a definite improvement in detergency upon the addition of a salt of celluronic acid in accordance with this invention.

Table II Alkyl aryl sulfonate (detergent 'C) lAlkyl aryl sulfonate (detergent 'C)+5% additive 79 Fatty acid soap (detergent D) (0.4% cone.) 9'2 Fatty acid soap (detergent D) (0.4% conc.)+5%

additive 105 Alkyl sulfonate (detergent E) Alkyl sulfonate (detergent E) +5% additive NOl-lOlliC alkyl phenol polyglycol ether (detergent Non-ionic alkyl phenol polyglycol ether (detergent 107 Y) +*5% additive utilized .vention for use in soft-water areas.

ent invention is that the celluronic acid salt be compatible with the organic surface-active detergent of the mixture; in-other words, that it be capable of dispersion or solution with the detergent.

Among the many detergent agents which may be improved by the application of the present invention, the alkaryl sulfonate-type detergents are found to constitute particularly suitable material capable of a striking improvement in detergency upon addition of small amounts of water-soluble .celluronic acid salts.

These alkaryl sulfonates applicable for the preparation of the detergent compositions of the present invention contain an alkyl chain of not less than 8 and not more than carbon atoms, directly linked to the aryl nucleus. Among these sulfonates, alkyl mononuclear aryl sulfonates, such as alkyl benzene sulfonates and alkyl toluene sulfonates, containing from not less than 8 to not more than 20 carbon atoms in the alkyl chain represent suitable ingredients for the preparation of the detergent compositions of the invention, a particularly desirable material being alkyl benzene sulfonates containing from 12 to 15 carbon atoms in the alkyl chain. These latter preferred sulfonates are obtained by alkylating benzene with polypropene, sulfonating the alkylate and neutralizing to form a water-soluble salt.

Although polypropenyl benzene sulfonates are preferred, other materials than polypropene, e. g., polybutene or chlorinated kerosene may be employed to alkylate the benzene ring prior to sulfonation and neutralization.

The improvement resulting from introduction 1 of water-soluble salts of celluronic acids may be in. detergent compositions containing builders as hereinbefore indicated. Exemplary builders are the alkali metal salts of inorganic acid such as alkali metal polyphosphates, including pyrophosphates, tri-polyphosphates, and tetraphosphates, alkali metal sulfates, alkali metal carbonates, bicarbonates, sesquicarbonates and their mixtures, alkali metal borates, alkali metal silicates, and the corresponding ammonium salts. In addition, salts introducing artificial hardness may be incorporated in the detergents of this in- Exemplary compounds are water-soluble salts of magnesium and calcium, such as magnesium sulfate, calcium nitrate or chloride, and the like. The proportion of builders normally incorporated in synthetic organic detergents, such as those of the sulfate and sulfonate types, is from about 60% to about 70%, although proportions as great as 80% and as small as 40% may be utilized. Compounds for producing artificial hardness normally are added in much smaller amounts, e. g., from 50 to 200 mol per cent based on the celluronic acid additive. However, the presence of the foregoing in- .insure a non-hygroscopic, nonwaking detergent product.

Generally, the proportion of sodium gency obtained with a 0.4%

sulfate in the detergent mixture, depending on the particular intended applicationof the detergent, varies from 0% to based on the total weight of-the dry sulfonate and sulfate ingredients, but preferably is greater than 50% and less than 80% by weight. The proportion of alkyl benzene sulfonate in the dry detergent mixture may be from 10% to by weight of the total dry sulfonatesulfate mixture (on additivefree basis, i. e., in the absence of the celluronic acid salt additive), and preferably less than 50% but at least 20% by weight. If so desired, other suitable inorganic alkali metal or ammonium salts, such as borates, phosphates, silicates, carbonates, and the like, may be incorporated as detergent extenders or builders. The alkali metal polyphosphates, such as tetrasodium pyrophosphate and sodium tetraphosphate, are particularly effective builders.

In the preparation of improved preferred detergent alkaryl sulfonate compositions of the present invention, an aqueous slurry, e. g., of sodium alkyl benzene sulfonate and sodium sulfate ingredients in a desired proportion is first prepared. Then at least 0.5 and preferably 3 and usually not more than about 5%, by weight based on the total dry ingredients of the detergent mixture of a sodium salt of celluronic acid is dispersed in this slurry in the required amount, and water is subsequently added, if necessary, to bring the concentration of the mixture to about 70% of water, whereupon the dry detergent is recovered by drum-drying. Of course, spraydrying and any other suitabletechnique of blending and recovering the improveddetergent composition may be likewise employed within the scope of the invention. The dried product represents an intimate mixture of sodium alkyl benzene sulfonate and sodium sulfate, having dispersed therein a small amount of a sodium salt of celluronic acid.

The various advantages of the improved compositions of the present invention, and particularly of the preferred alkaryl sulfonate-type compositions are brought to light by the examination of experimental data presented hereinafter in the form of tables and graphs. The tests illustrated by these data are effected under conditions similar to those used in tests of Tables I and II. However, the amount of the sodium salt of celluronic acids added to improve detergency is equal to 3% by Weight, unless otherwise indicated. The preferred alkyl benzene sulfonate detergent of the invention, containing from 12 to 15 carbon atoms in the alkyl chain and produced by alkylating the benzene ring with poly propene, comprises 40 parts of sodium alkyl benzene sulfonate to 60 parts of sodium sulfate on additive-free basis and similarly to Tables I and II is designated as detergent A. Other designations of the various compositions tested are also the same as in Tables I and II.

In tabulating and plotting the experimental data, the detergency ratings iorvarious deteng'ents are computed either in terms of the percentage'of soil removal or with reference to one of the two arbitrarily chosen standards: (1) detergency obtained with a 0.2% concentration of alkyl sulfate (detergent B) in hard water (300 parts per million), assumed to be equal 100 and designated as Detergent Index; and (2) deterconcentration of soap D in hard water (300 parts per million), which has been used as a standard in Tables I and II hereinbefore.

Table III shows the differences in the improvement in detergency of the alkyl benzene sulfonate (detergent A) of the present invention, occasioned by the addition of 3% by weight of sodium salt of celiuronic acids of varying carboxyl content. The existence of an optimum range of carboxyl content is readily perceived.

As the additive used alone is found to have no detergent action in launderometcr tests, the detergency improvement brought about by its presence in alkyl benzene sulfonate detergent mixture A is clearly evidenced by the above data in Table V.

Table VI contains the results of launderometer tests for varying total concentration of the Tabl 1]] improved detergent mixture and shows the in- [97% alkaryl sulfonate (detergent A)+3% additive] l0 creae m detergenfiy s f from intro duction of celluronic acid additive upon increassoap Detergent ing the total concentration of the detergent Oarboxyl Content in Per Cent by Weight Index Index m1xture T Table VI 7.0- 91 121 sis is Per cent 19.5 s2 12:; Soap 20.6- 76 116 Sample 10o Alk The data on soil removal assembled in Table IV gg} ggfiggggi ig gggig g 13222 24 again clearly show the existence of an optimum additive 89 1007 Alkar lsulfoiiate Deter ent A alone .20 69 range of carboxyl-content between about 11.5% Aikeriyi sulfonate (Det rgent A)+3% t 1 5% additive .20 102 100% Alkaryl sulfonate (Detergent A) alone 30 71 97% Alkaryl sulfonate (Detergent A)+3 Table IV additive .30 107 100% Alkaryl sulfonate (Detergent A) alone- 40 64 97%id glkaryl sulfonate (Detergent A)+3% Carbox 1 a i We .40 110 (lonten t gg in Per {lent Removal by Wing The next Table VII illustrates the efiect of 9 Mk 1 u t D t t A salts of celluronic acids on the detergency of 4 3 M 62 various commercial products in hard water. All 97% Alkaryl sulfonate (Detergent A), of the compositions tested show an improvement +3% Addlm'e 65 in deter enc in the resen e f th ddit' 97% Alkaryl sulfonate (Detergent A), p C 0 8 new a We ;a 7 i i daitive HH H 20.6 64 85 of the invention. However, a truly remarkable 9 j' f l iffff ffffif f m improvement is observed for alkyl benzene sulfo- 977 Alkaryl suli'oiiate Detergent A) t g gli g 5 t 1 1L 5 65 na e detergents A and C i any s e ergen 3% Additive 16 2 "66 Table VII 97% Alkai'yl s +3% Additive '62 40 il rv s fl mg dk sg alone Per cent soap y S 3. 9 e ergen a 0118"..-- Soap (D) (0.4% cone.) alone 61 Composltlon Eggs; Index *in tests marked with an asterisk, a purc ased cell p Alkaryl sulfonate (Detergent A) .2 44 additive is used, while the remainder of tests employ a similar Alkaryl flfon te (Detergent A)+3% ti ,2 3 additive prepared in the laboratory. 45 Alkyl sulfate (Detergent B) 2 42 sulf1ate11(fDet1erg(%ittB) +3t%oa)dditive 2 64 In Table V are tabulated the values of soil re- Y 5 0112 e 9 37 Alkl lull t DtetC3 moval in per cent obtained in still another series ims?"jNi? i f f if% i lfi ?3 2 61 of tests. A 0.2% concentration of alkaryl sulfo- 508p (D) concentratiml) 62 l S D 0.4 concentration 3 additive .4 68 nate (detergent A) is again used, and increasing o increments of the sodium salt of celluronic acid are added thereto. The carboxyl content of the additive is from about 11.5% to about 18.5% by weight.

Table V Total Concentration in per Per cent Sample cent (Deter- Soil Regentl-Addimoval two) 100% Alkaryl sulfonate (Detergent A) alone 0.200 51 100% Alkaryl sulfonate (Detergent A)+0.5% additive 0. 201 57 100% Alkaryl sulfonate (Detergent A)+1.0% additive 0. 202 61 100% Alkaryl sulfonate (Detergent A) +20% additive 204 63 100% Alkaryl sulfonate (Detergent A)+3i0% additive 206 66 100% Alkaryl sulionate (Detergent A) +40% additive 208 66 100% Alkaryl sulfonate (Detergent A)+8.0% additive- 216 65 100% Alkaryl sulfona A)+10.0% additive 220 65 100% Alkaryl siilfonate (Detergent A +15.0% additive .230 63 Alkyl sulfate (Detergent B) alone 0. 2 42 Table VIII contains additional data from similar tests with various commercial detergents, the detergency being evaluated in this instance in terms of the Soap Index mentioned hereinbefore. Here again the improvement occasioned by the presence of the celluronic acid additive is clearly Table IX is introduced to show that the benefits obtained by the use of the salts of celluronic acids in alkyl benzene sulfonate detergent compositions are not limited to the particular 40/60 ratio 0 sufonate to sulfate.

1 l Table IX Per cent Soil Sample Removal (97% suli'onate+3% additive)+40% NszSO 50% (97% sulfonate+3% additive)|50% N azSOi. 40% sulionate (no additive) +60% NazSO4 40% (07% sulfonate+ 3% additive) +00% N azS O4 30% sult'onate (no additive) +70% NazS O4 30% (97% sulionate+3% additivc)+70% N11230:

Detergent index 1.00% detergent (no additive) 91 100% detergent+$% additive 1'72 90% detergent (no additive) +10% NalPzOL 104 99% detergent-|-3% additive+l0% NarPzOv- 143 It is to be noted that since the alkyl benzene detergent mixture used for these tests has the sulfonate/ sulfate ratio of 40/ 60, the proportion of surface-active organic detergent will be further reduced upon continued increase in the propor-= tion of builders such as tetrasodium pyrophosphate. In order to obtain the benefits of the invention with detergent mixtures containing larger amounts of builders, it may be further necessary to increase the amount of detergent mixture added to the cleansing solution. In other words, when the effective concentration of the surfaceactive agent is reduced to a very low figure, such as less than 0.1% concentration in the cleansing water solution, the detergent power of the solu tion may be so depreciated as to mask the beneficial eiIects of the water-soluble celluronic acids. On the other hand, concentration of surfaceaetive organic detergents in the cleansing water solution need not exceed about 0.5% by weight although higher concentrations are notpreeluded.

An additional series of tests is carried out to determine in terms of the Soap Index used hereinbeiore the improvement in detergency brought about by the application of the improved compositions of the present invention to the removal of vacuum-cleaner dust-type soil from hard twisted cotton. This type of soil is obtained in the collector bags of conventional vacuum cleaners from cleaning rugs, overstufied furniture and drapes. Same test conditions are applied as above, the hardless of water being 50 parts per million. The results are given in Table XI.

Table XI Soap index Non-ionic alkyl phenol polyglycol ether (detergent Y) 90 Non-ionic alkyl phenol polyglycol ether detergent Y) additive 94' Alkenyl dicarboxylic acid (detergent X) 90 Alkenyl dicarboxylic acid (detergent X) 5% additive 106 Alkaryl sulfonate (detergent A) '74 Alkaryl sulfonate (detergent A) 5% additive 88 t is also observed that the addition of the sodium salt of celluronic acid enhances the removal of soil from wool fabric. A series of tests are carried out on W001 soiled with an oily-type soil at 85 F. The hardness of water is 300 parts per million. The results indicate that there is an increase in soil removal averaging 5%. These results are tabulated in Table XII.

Table XII Oonceng i Y I 01 anon Removal 100% Alkaryl sull'onate (Detergent A) .1 .15 8

97% Alkaryl sulfonate (Detergent A)+3% additive 15 10 100% Alkoryl sulfonate (Detergent A) .20 1G 97% Alkaryl sulionate (Detergent A)+3% additive 20 22 100% Alkaryl sulfonatc (Detergent A) .30 49 97% Alkaryl sultonate (Detrgent A)+3% additive 30 46 100% Alkaryl sulfonate (Detergent A) 40 47 97% Alkaryl sull'onate (Detergent A)-l-3% additive 40 50- The foregoing experimental, data relate at least primarily to improvements obtainable with Water-soluble alkali metal salts of celluronic acid. Operativeness of a Wide variety of-other watersoluble salts of celluronic acid as hereinbefore disclosed is established by the data tabulated in Table XIII. It will be observed that similar remarkable improvements in detergency are obtained by adding both monoand bivalent watersoluble salts of celluronic acids to detergent mixtures. These salts embrace both the alkali and alkaline earth metals as well as non-metallic salts, such as amine and quaternary ammonium salts oi eelluronic acid. The tests represented by the data 0;" Table XIII are launderometer tests for oily soil removal from hard twisted cotton swatches at 140 F. under standard conditions in distilled water and in hard water (300.;oarts per million), using alkaryl sulfonate (detergent A) detergent of the preceding tests (40 parts of sodium alkyl benzene sulfonate to 60 parts of sodium sulfate on additive-free basis). A 0.2% concentration of the detergent mixture in water is maintained, while the water-soluble eelluronic acid salt is present in an amount equal to 5% by weight of the total concentration of dry ingredients in the detergent mixture. The detergency ratin s are again computed with reference to a whiteness level obtained with a 0.4% concentration of a well-known soap in hard water, assumed to be equal to 100 and designated as Soap Index.

It will be understood that the addition of monovalent cationic salts ofcelluronicacids,

such as sodium celluronate, to dilute solutions of non-cationic detergent mixtures in hard water, results in the formation of magnesium and calcium celluronates which correspondingly improve the detergency of such hard-water solutions.

Table XIII Soap Index Distilled Hard Water Water Detergent A clone (average of 2 runs) 68 79 95% detergent A+5% sodium celluronate 108 98 95% detergent A+5% potassium celluronata." 111 92 95% detergent A+5% lithium eelluronate 104 115 95% detergent A+5% magnesium eelluronate. 106 detergent A+5% ammonium eelluronate... 107 82 95% detergent A+5% benzyl trimethyl ammonium celluronate .1 104 122 95% detergent A+5% tetramethyl ammonium eelluronate 108 95% detergent A+5% ethanolamine celluronatc -1 110- 95 95% detergent A+5% dicthanolamine celluronate 107 97 95% detergent A+5% triethanolamine celluronate 107 94' 95% detergent A+5% morpholine eelluronate..- 110 92 95 7 detergent A+5% piperidinc eelluronatenn 108 113 95 0 detergent A+5% pyridine eelluronate 110 116 The invention is further illustrated by several figures which translate into graphs some of the data tabulated hereinbefore. Figure 1 graphically represents the data of Table III and establishes the existence of an optimum range of carboxyl content between about 11.5 to about 18.5% by weight based on the weight of a celluronic acid molecule for a representative detergent composition containing 97% of sodium alkyl benzene sulfonate/sodium sulfate mixture and 10 3% of sodium celluronate. Figure 2 corresponds to the data in Table V and illustrates the effect of varying celluronate concentrations upon the extent of soil removal by typical alkaryl sulfonate detergent (detergent A).

Whenever desired, the I beneficial effect of water-soluble celluronates on the detergency characteristics of the compositions of the present invention may be further enhanced by combining celuronate additives with other surface-active additives derived from cellulosic materials, such as carboxy methyl cellulose, hydroxy ethyl cellulose, and water-soluble ethers of cellulose, e. g., methyl ether. It will be also noted that various organic oxygen-containing solubilizers, e. g., polyethyl alkylenes, which may be used in detergent mixtures for cleaning heavily soiled, greasy surfaces, when present in the corresponding anionic and non-ionic detergent mixtures of the present invention containing water-soluble salts of celluronic acid, do not decrease, but, on the contrary enhance the detergency effect of the celluronic acid salts.

.As indicated hereinbeiore, the water-soluble salts of celluronic acids effective in raising the detergency characteristics of organic surfaceactive detergents and of compositions containing the same, may be incorporated therewith by direct addition, whereupon the mixtures are dried and are made available to the user in dry form, such as flakes or beads. In some cases, however, it will be preferred to prepare the detergent mixtures containing dispersed watersoluble celluronic acid salts in the form of concentrated solution; for instance, suitable concentrated mixtures containing sulfonate or sulfate detergents with water-soluble celluronates intimately distributed therein may be prepared, the ratio of celluronic acid salts to sulfonate or sulfate detergents in such concentrates being from about 1:1 to 1:10'in parts by weight. The availability of detergent compositions of the present invention in the form of concentrates offers a number of advantages, the principal ones being the ease of handling for shipping purposes, and a greater accuracy in adding the amount required for the corresponding ultimate application.

The invention as described in this specification is not restricted ,to the detergent compositions containing alkali metal salts of celluronic acids but also includes detergent compositions which comprise other wholly or partly soluble salts of celluronic acids produced by dissolving these acids in dilute ammonia, warm aqueous pyridine, aqueous solutions of ammonium hydroxides, and the like.

The valuable improved detergent compositions of this invention, whether in dry form as flakes or beads, or in the form of concentrates, are suitable for a number of applications, namely, for laundering of textile fabrics and similar materials, in washing automobiles, various painted- In conclusion, it is to be understood that the aforegiven description and the experimental data are intended to be illustrative only and that any variation or modification of the invention, which conform with the spirit and the scope thereof, are intended to be included within the terms of the appended claims.

I claim: 1

1. A detergent composition comprising a watersoluble salt of a celluronic acid, having a carboxyl content from about 7 to about 20% by weight based on the acid, and an alkaryl sulfonate detergent containing from 8 to 20 carbon atoms in the alkyl chain, said water-soluble salt of a celluronic acid being present in a minor amount sufiicient to enhance the detergency characteristics of said sulfonate detergent, and said amount being from at least 1% to less than 50% by weight based on the surface active alkaryl sulfonate component of said alkaryl sulfonate detergent.

2. A detergent composition comprising a watersoluble salt of a celluronic acid, having a carboxyl content from about 7 to about 20% by weight based on the acid, and an alkyl benzene sulfonate detergent containing from 8 to 20 carbon atoms in the alkyl chain, said detergent being present in an amount sufi'icient to provide effective cleansing action in Water solution, said water-soluble celluronic acid salt being present in a minor amount suificient to enhance the detergency characteristics of said solution, and the weight ratio of said celluronic acid salt to said alkyl benzene sulfonate detergent in said solution being from about 1:1 to about 1:10.

3. A detergent composition comprising a watersoluble salt of a celluronic acid, having a carboxyl content from about 11.5 to about 18.5% by weight based on the acid, and an alkyl benzene sulfonate detergent containing from 12 to 15 carbon atoms in the alkyl chain, said alkyl benzene sulfonate detergent being present in an amount sufficient to provide efiective cleansing action in water solution, said water-soluble celluronic acid salt being present in a minor amount sufficient to enhance the detergency characteristics of said solution, and the weight ratio of said "water-soluble celluronic acid salt to said alkyl benzene sulfonate detergent in said solution being from about 1:1 to about 1:10.

4. A detergent composition comprising a watersoluble salt of a celluronic acid, having a carboxyl content from about '7 to about 20% by weight based on the acid, and an alkaryl sulfonate detergent having from 8 to 20 carbon atoms in the alkyl chain, said alkaryl sulfonate detergent being present in amounts suificient to provide efiective cleansing action in water solution, and said water-soluble celluronic acid salt being present in a minor amount suflicient to enhance the detergency characteristics of said solution, the weight ratio of said Water-soluble celluronic acid salt to said alkaryl sulfonate detergent in said solution being from about 1:1 to about 1 10.

5. A detergent composition comprising a watersoluble salt of a celluronic acid, having a carboxyl content from about 11.5 to about 18.5% by weight based on the acid, and an alkaryl sulfonate detergent having from 12 to 15 carbon atoms in the alkyl chain, said alkaryl sulfonate being present in an amount sufiicient to provide efiective cleansing action in water solution, and said water-soluble celluronic acid salt being present in a minor amount suflicient to enhance the detergency characteristics of said solution,

the weight ratio of water-soluble acid salt to said alkaryl sulfonate detergent in said solution being Numb r from about 1: 1 to about 1: 10. 2 232 3 JOHN E. HANSON. 213473336 REFERENCES CITED 0 The following references are of record in the Number file of this patent: 211,294-

UNITED STATES PATENTS Name Date Yackel et a1 Feb. 25, 1941 Seyferth Apr. 26, 1944 FOREIGN PATENTS Country Date Great Britain Feb. 2 1, 1924 

1. A DETERGENT COMPOSITION COMPRISING A WATERSOLUBLE SALT OF A CELLURONIC ACID, HAVING A CARBOXYL CONTENT FROM ABOUT 7 TO ABOUT 20% BY WEIGHT BASED ON THE ACID, AND AN ALKARYL SULFONATE DETERGENT CONTAINING FROM 8 TO 20 CARBON ATOMS IN THE ALKYL CHAIN, SAID WATER-SOLUBLE SALT OF A CELLURONIC ACID BEING PRESENT IN A MINOR AMOUNT SUFFICIENT TO ENHANCE THE DETERGENCY CHARACTERISTICS OF SAID SULFONATE DETERGENT, AND SAID AMOUNT BEING FROM AT LEAST 1% TO LESS THAN 50% BY WEIGHT BASED ON THE SURFACE ACTIVE ALKARYL SULFONATE COMPONENT OF SAID ALKARYL SULFONATE DETERGENT. 